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1. Introduction
Liquid Alum is a solution of aluminum sulfate having the general chemical
formula Al2(SO4)3.xH2O. For many years, 17% alum in solid form was easy to
package and economical to ship over long distances. However, liquid alum has
become more popular now because of its lower cost in handling and storage.
Several processes have been suggested for producing aluminum sulfate
from clay. Most of the reported processes include calcination of clay before
extracting alumina by treatment with sulfuric acid. In most reported literature,
the effect of clay grinding before calcination was not paid enough attention.
Some of the reported literature recommended calcination temperature of 790oC
[1] or 770- 820oC [2]. Others [3] reported a recommended temperature of 550oC
and mentioned that if kaolin is not heated, the solubility vanishes. It was
reported [4] that kaolin is not markedly affected by previous ignition of the
sample, but ignition of the mineral pyrophyelite (Al2O3. 4 SiO2.H2O) causes a
marked increase in alumina extraction. It was also reported that heating at 700
800oC for one hour could be practiced if alumina is extracted from highly
aluminous clays [5]. When sulfuric acid was added to kaolin prior to heating,
the calcination temperature was about 850oC [6]. Pressure was applied after
heating kaolin to 600oC to extract aluminum oxide [7].
Different concentrations of sulfuric acid were reported for extraction of
alumina from calcined clays. It was reported that, in general, the extraction of
alumina from calcined clays increases with increasing duration of extraction at a
fixed temperature and also increases by increasing temperature at a fixed
duration of extraction. Concentration of about 70 wt.% H2SO4 has been
patented to produce aluminum sulfate [8]. When kaolin was heated to 1100
1200oC for one hour, then boiling calcined kaolin with sulfuric acid of
concentration 5 7 wt.% H2SO4 for one hour, alumina extraction was about
80% [9]. Leaching with sulfuric acid was practiced at 90oC and 10 20 % acid
concentration [10]. Another patent reported 30 wt. % acid concentration as the
recommended concentration [11]. A temperature of 105oC has been reported [8]
as a recommended extraction temperature. Another patent recommended a
temperature of 70 90oC for 10 12 hours to extract 70 80 % of alumina
[12].
Other articles were reported for the production of aluminum sulfate for
different types of clays [13-20], from aluminum industry wastes [21-24] or from
different industrial wastes [25-29]. The use of amines for extracting iron from
aluminum sulfate leach liquor was also reported [30-31].]
In this paper, the possibility of manufacturing liquid alum from Saudi
clays to satisfy local demands of coagulant aluminum sulfate which are
extremely abundant in the Kingdom will be investigated. A bench scale study
was carried out to investigate the activation of Saudi clay by calcination method
and the leaching of alumina from the calcined clay by treatment with sulfuric
acid. The effect of different variables on both activation and leaching steps is
investigated to recommend the most effective conditions for both processes.
2. Materials And Methods
2.1 Materials
The clay samples used in this study is native kaolinitic clay obtained
from Az-Zabirah area. Chemical analysis of the ground clay sample was carried
out according to the standard methods [32,33]. The analysis is given in Table 1.
The sulfuric acid used was BDH general purpose reagent.
Table 1. Chemical Composition of Local Kaolinitic Clay
Compound
SiO2
Al2O3
29.4
Fe2 O3
2.87
TiO2
MgO
CaO
K2O
1.17
Na2O
2.11
MnO
SO3
< 0.05
< 0.05
P2O5
L.O.I.
< 0.05
0.35
0.59
0.17
16.02
2.2 Experimental
The equivalent diameter of the raw local clay sample was about 2 to 3
inches. The clay sample was ground using a ball mill to pass a sieve of a
specified mesh number ranging from 8 to 200 mesh (standard Tyler screens).
For each standard sieve, the ground clay sample was placed on the sieve, and
then mechanically shaked for 5 minutes. The oversize was further ground
followed by sieving on the same sieve. The procedures were repeated till the
entire clay sample passed through the sieve.
Twenty five grams of the ground clay sample were subjected to
calcination. A muffle furnace with a maximum temperature of 1200oC was
100
90
80
Percent Extraction
70
60
50
40
30
20
Alumina
Iron oxieds
10
0
0
50
100
150
200
250
These results indicate that grinding the clay samples beyond 48 mesh has
no significant effect on the extraction of alumina from local clay sample. This
indicates that the grain size of -48 to-52 mesh is quite suitable for grain size to
be used. This will also benefit in reducing excessive grinding cost. A grain size
of 65 mesh was selected for further work.
3.2 Effect of Temperature and Time of Calcination
The effect of varying duration and temperature of calcination on the
percent extraction of alumina and iron oxide is indicated in Tables 2 and 3 and
Fig. 2. The data indicate the following points:
100
90
80
Percent Extraction
70
60
50
40
30
Al2O 3
Fe2O 3
20
10
0
500
600
700
800
900
1000
Temperature C
i.
ii.
iii.
An inert zone below 450 oC, during which the percent extraction of
alumina is small.
A promising zone from 500 oC to 750 oC during which percent
extraction of alumina increases. The percent extraction decreases
sharply when the temperature exceeds 800 oC.
The highest alumina extraction (91.1%) is reached at a calcination
temperature of 750 oC and for a duration time of one hour as can be
seen from Table (1). However the increase in percentage of alumina
extraction when temperature increases from 700 to 750 oC is only 0.2
%. This slight increase does not justify the corresponding increase in
energy requirement. Therefore, a temperature of 700 oC is
recommended for further experimental work.
10
90
Percent Extraction
80
70
60
50
Al2O3
40
30
10
Fe2O3
20
30
40
Concentration of H2SO4
( %)
50
60
70
11
50
40
30
50%
20
60%
70%
80%
90%
100%
10
110%
120%
0
0
Figure 4. Effect of extraction time on % Fe2O3 extraction at different acid to clay ratios.
Grain size: -65 mesh standard Tyler screens, calcination at 700 o C.
12
60
50
40
30
50%
20
60%
70%
80%
10
90%
100%
110%
120%
0
0
Figure 5. Effect of extraction time on % Fe2O3 extraction at different acid to clay ratios.
Grain size: -65 mesh standard Tyler screens, calcination at 700 o C for 1 hr
and leaching with 40% by wt. H2SO4 at boiling conditions.
Figure (8) shows a comparison between the theoretical and actual percent
extractions for Al2O3 and Fe2O3. Acid to clay ratio above 120% does not appear
to give any sign of increase in the yield of alumina. The point of intersection
between the straight line, representing the theoretical conditions and the
experimental curve, corresponds to 88.1% acid to clay ratio and 88.6% alumina
extraction, which means complete reaction of the acid added with alumina in
the clay. Acid to clay ratio above 88.1% results in the presence of free unreacted
acid. Acid to clay ratio below 88.1% shows higher values than those expected
theoretically which indicates that such solutions of extracted aluminum sulfate
contain dissolved alumina. Analysis of the liquor obtained after filtration gives
17% Al2O3 content whereas analysis of combined filtrate and washing gives
8.1% Al2O3, which is within the commercial requirements for liquid alum to
avoid crystallization of aluminum sulfate and therefore no concentration step
needed.
13
10
90
80
70
1/14 hr
60
1/2 hr
1 hr
2 hrs
3 hrs
50
40
30
50
70
90
110
Acid: clay ratio (% of stoichiometric)
130
Figure 6. Effect of acid to clay ratio on extraction of Al2O3 at different leaching periods.
Grain size: -65 mesh standard Tyler screens, calcination at 700 o C for 1 hr
and leaching with 40% by wt. H2SO4 at boiling conditions.
14
50
40
30
20
1/14 hr
1/2 hr
1 hr
t2 hrs
3 hrs
10
20
40
60
80
100
12
Acid: clay ratio (% of stoichiometric)
140
Figure 7. Effect of acid to clay ratio on extraction of Fe2O3 at different leaching periods.
Grain size: -65 mesh standard Tyler screens, calcination at 700 o C for 1 hr
and leaching with 40% by wt. H2SO4 at boiling conditions.
100
90
80
Percent Extraction
70
60
50
40
30
20
Al2O3
Fe2O3
Theo
10
0
30
50
70
90
110
130
15
Leaching the Saudi clay at the above conditions will result in 89.5 %
extraction of the alumina content in the clay. The product liquid alum contains
8.1% Al2O3 which corresponds to about 23.4% Al2(SO4)3.
Acknowledgement: This work was supported by Scientific Research Council,
King AbdulAziz University (Jeddah, Saudi Arabia) under grant number
119/422.
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